PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
7
(br s, 1H, ꢂNH), 4.40-4.36 (m, 1H, ꢂCH¼) , 4.21-4.11 (m, (E)-diethyl (1-((2,5-dichlorophenyl)amino)-3-phenylallyl)-
phosphonate (4 g)
4H, 2 ꢁ ꢂOCH2CH3), 2.39 (s, 3H, ꢂSCH3), 1.33-1.28 (m,
6H, 2 ꢁ ꢂOCH2CH3) ppm; 13C NMR (100 MHz, CDCl3): d
Light yellow oily mass; yield: 84% (87 mg; 0.25 mmol scale);
1H NMR (400 MHz, CDCl3): d ¼ 7.49-7.46 (m, 2H, Ar-H),
7.44-7.40 (m, 2H, Ar-H), 7.37-7.33 (m, 1H, Ar-H), 7.31-7.27
(m, 1H, Ar-H), 6.81-6.74 (m, 3H, 2 ꢁ Ar-H and 1 ꢁ
ꢂCH¼), 6.41-6.32 (m, 1H, ꢂCHPO), 5.12-5.09 (m, 1H,
ꢂNH), 4.59-4.49 (m, 1H, ꢂCH¼), 4.33-4.28 (m, 4H, 2 ꢁ
ꢂOCH2CH3), 1.45-1.38 (m, 6H, 2 ꢁ ꢂOCH2CH3) ppm; 13C
NMR (100 MHz, CDCl3): d ¼ 143.49 (d, JCP ¼ 11 Hz),
¼ 145.44, 136.24 (d, JCP ¼ 15 Hz), 133.23 (d, J2 ¼ 5 Hz),
CP
133.12, 131.10, 130.93, 128.61 (d, JCP ¼ 17 Hz), 128.03,
127.86, 126.62 (d, JCP ¼ 15 Hz), 126.05, 123.39 (d, J3
5 Hz), 123.20, 114.51 (d, JCP ¼ 17 Hz), 63.62 (d, J2
¼
¼
CP
CP
7 Hz, ꢂOCH2CH3), 63.22 (d, J2
¼ 7 Hz, ꢂOCH2CH3),
CP
54.23 (d, J1 ¼ 153 Hz, ꢂCHPO), 18.78 (ꢂSCH3), 16.62 (d,
CP
¼ 5 Hz, ꢂOCH2CH3), 16.57 (d, J3
J3
¼ 5 Hz,
CP
ꢂCOPCH2CH3) ppm; 31P NMR (162 MHz, CDCl3):
d
136.10, 133.70, 133.23 (d, J2
¼ 12 Hz), 130.09 (2 C),
CP
128.74 (2 C), 128.22, 126.81 (2 C), 122.34 (d, J3 ¼ 5 Hz),
CP
22.13 ppm; Elemental analysis: calcd (%) for C20H26NO3PS:
C, 61.36; H, 6.69; N, 3.58; found: C, 61.32; H, 6.67; N, 3.59.
118.34 (d, JCP ¼ 22 Hz), 112.45, 63.83 (d, J2
¼ 7 Hz,
CP
ꢂOCH2CH3), 63.41 (d, J2 ¼ 7 Hz, ꢂOCH2CH3), 53.91 (d,
CP
J1
¼
153 Hz, ꢂCHPO), 16.62 (d, J3
¼
5 Hz,
ꢂCOPCH2CH3), 16.57 (d, J3
¼ 5 Hz, ꢂOCH2CH3) ppm; 31P
CP
CP
(E)-diethyl (1-((3-(methylthio)phenyl)amino)-3-phenylallyl)-
phosphonate (4e)
NMR (162 MHz, CDCl3): d 20.81 ppm; Elemental analysis:
calcd (%) for C19H22Cl2NO3P: C, 55.09; H, 5.35; N, 3.38;
found: C, 55.01; H, 5.33; N, 3.40.
Pale yellow semi-solid; yield: 77% (75 mg; 0.25 mmol scale);
1H NMR (400 MHz, CDCl3): d ¼ 7.35 (d, J ¼ 7.6 Hz, 2H,
Ar-H), 7.31-7.27 (m, 2H, Ar-H), 7.24-7.21 (m, 1H, Ar-H),
7.08 (t, J ¼ 8.0 Hz, 1H, Ar-H), 6.73-6.68 (m, 1H, ꢂCH¼),
6.64 (d, J ¼ 7.6 Hz, 1H, Ar-H), 6.61 (t, J ¼ 2.0 Hz, 1H, Ar-H),
6.48 (dd, J ¼ 6.4, 2.4 Hz, 1H, Ar-H), 6.28-6.22 (m, 1H,
ꢂCHPO), 4.52-4.43 (m, 2H, ꢂNH & ꢂCH¼), 4.23-4.11 (m,
4H, 2 ꢁ ꢂOCH2CH3), 2.43 (s, 3H, ꢂSCH3), 1.33-1.28 (m,
6H, 2 ꢁ ꢂOCH2CH3) ppm; 13C NMR (100 MHz, CDCl3): d
¼ 147.04 (d, JCP ¼ 13 Hz), 139.52, 136.33 (d, JCP ¼ 3 Hz),
(E)-diethyl (3-phenyl-1-((4-(trifluoromethyl)phenyl)ami-
no)allyl)phosphonate (4 h)
Brownish semi-solid; yield: 75% (78 mg; 0.25 mmol scale);
1H NMR (400 MHz, CDCl3): d ¼ 7.35 (d, J ¼ 8.4 Hz, 2H,
Ar-H), 7.29 (d, J ¼ 7.6 Hz, 2H, Ar-H), 7.26-7.22 (m, 2H, Ar-
H), 7.20-7.16 (m, 1H, Ar-H), 6.66 (d, J ¼ 8.8 Hz, 2H, Ar-H),
6.61 (dd, J ¼ 5.0, 1.2, 0.8 Hz, 1H, ꢂCH¼), 6.22-6.16 (m, 1H,
ꢂCHPO), 4.75-4.67 (m, 1H, ꢂNH), 4.49-4.39 (m, 1H,
ꢂCH¼), 4.18-4.04 (m, 4H, 2 ꢁ ꢂOCH2CH3), 1.28-1.22 (m,
6H, 2 ꢁ ꢂOCH2CH3) ppm; 13C NMR (100 MHz, CDCl3): d
¼ 149.27 (d, JCP ¼ 12 Hz), 136.11 (d, JCP ¼ 3 Hz), 133.45
133.19 (d, J2
¼ 13 Hz), 129.69, 128.65 (2 C), 128.19,
CP
127.98, 126.68, 123.37 (d, J3
¼ 4 Hz), 116.75, 111.80,
CP
110.79, 63.62 (d, J2 ¼ 7 Hz, ꢂOCH2CH3), 63.19 (d, J2
CP
CP
¼ 8 Hz, ꢂOCH2CH3), 54.98 (d, J1 ¼ 153 Hz, ꢂCHPO),
(d, J2 ¼ 12 Hz), 128.74 (2 C), 128.21 (2 C), 126.79, 126.73
CP
CP
16.59 (d, J3 ¼ 5 Hz, ꢂOCH2CH3), 16.15 (d, J3 ¼ 73 Hz,
(2 C, d, JCP ¼ 3 Hz), 123.54, 122.62 (d, J3 ¼ 5 Hz), 120.25
CP
CP
CP
ꢂOCH2CH3), 15.78 (ꢂSCH3) ppm; 31P NMR (162 MHz,
CDCl3): d 22.16 ppm; Elemental analysis: calcd (%) for
C20H26NO3PS: C, 61.36; H, 6.69; N, 3.58; found: C, 61.30;
H, 6.67; N, 3.55.
(d, JCF ¼ 32 Hz, ꢂCF3), 113.06 (2 C), 63.69 (d, J2 ¼ 7 Hz,
CP
ꢂOCH2CH3), 63.39 (d, J2 ¼ 7 Hz, ꢂOCH2CH3), 53.68 (d,
CP
J1
¼
154 Hz, -CHPO), 16.61 (d, J3
¼
4 Hz,
ꢂCOPCH2CH3), 16.57 (d, J3 ¼ 5 Hz, ꢂOCH2CH3) ppm; 19F
CP
CP
NMR (376 MHz, CDCl3): d ꢂ 61.22 ppm; 31P NMR
(162 MHz, CDCl3): d 21.65 ppm; Elemental analysis: calcd
(%) for C20H23F3NO3P: C, 58.11; H, 5.61; N, 3.39; found: C,
58.01; H, 5.59; N, 3.37.
(E)-diethyl (1-((4-bromophenyl)amino)-3-phenylallyl)-
[16c]
phosphonate (4f)
Light yellow semi-solid; yield: 76% (81 mg; 0.25 mmol scale);
1H NMR (400 MHz, CDCl3): d ¼ 7.34 (d, J ¼ 7.6 Hz, 2H,
Ar-H), 7.30-7.27 (m, 2H, Ar-H), 7.25-7.21(m, 3H, Ar-H),
6.69-6.64 (m, 5.2, 1H, ꢂCH¼), 6.59-6.57 (m, 2H, Ar-H),
6.26-6.21 (m, 1H, ꢂCHPO), 4.44-4.37 (m, 2H, ꢂNH &
ꢂCH¼), 4.19-4.09 (m, 4H, 2 ꢁ ꢂOCH2CH3), 1.34-1.27 (m,
6H, 2 ꢁ ꢂOCH2CH3) ppm; 13C NMR (100 MHz, CDCl3): d
¼ 145.67 (d, JCP ¼ 12 Hz), 136.18 (d, JCP ¼ 2 Hz), 133.27
(E)-diethyl(1-((3,5-bis(trifluoromethyl)phenyl)amino)-3-phe-
nylallyl)phosphonate (4i)
White powder; mp: 136-138 oC; yield: 76% (92 mg;
0.25 mmol scale); 1H NMR (400 MHz, CDCl3): d ¼ 7.31-
7.28 (m, 3H, Ar-H), 7.24-7.19 (m, 2H, Ar-H), 7.15 (s, 1H,
Ar-H), 7.08 (br s, 2H, Ar-H), 6.73-6.68 (m, 1H, ꢂCH¼),
6.23-6.16 (m, 1H, ꢂCHPO), 5.43-5.39 (m, 1H, -NH), 4.53-
4.43 (m, 1H, ꢂCH¼), 4.23-4.09 (m, 4H, 2 ꢁ ꢂOCH2CH3),
1.33-1.25 (m, 6H, 2 ꢁ ꢂOCH2CH3) ppm; 13C NMR
(100 MHz, CDCl3): d ¼ 147.71 (d, JCP ¼ 11 Hz), 135.99 (d,
(d, J2 ¼ 13 Hz), 132.07 (2 C), 128.67 (2 C), 128.06, 126.65
CP
(2 C), 123.02 (d, J3 ¼ 4 Hz), 115.48 (2 C), 110.29, 63.59 (d,
CP
7 Hz, ꢂOCH2CH3), 63.22 (d, J2
J2
¼
¼
7 Hz,
CP
ꢂCOPCH2CH3), 54.12 (d, J1 ¼ 154 Hz, ꢂCHPO), 16.59 (d,
JCP ¼ 3 Hz), 134.09 (d, J2 ¼ 13 Hz), 132.56 (2 C, 2 ꢁ
CP
5 Hz, ꢂOCH2CH3), 16.54 (d, J3
CP
J3
¼
¼
5 Hz,
–CF3), 128.78 (2 C), 128.35 (2 C), 126.70 (2 C), 121.91 (2 C,
ꢂCOPCH2CH3) ppm; 31P NMR (162 MHz, CDCl3):
d
CP
d, J3 ¼ 5 Hz), 113.09 (2 C, d, JCP ¼ 2 Hz), 111.32, 63.72
CP
(d, J2
¼ 7 Hz, ꢂOCH2CH3), 63.58 (d, J2
¼ 8 Hz,
21.92 ppm; Elemental analysis: calcd (%) for C19H23BrNO3P:
C, 53.79; H, 5.46; N, 3.30; found: C, 53.71; H, 5.44; N, 3.31.
CP
CP
ꢂOCH2CH3), 53.74 (d, J1 ¼ 154 Hz, ꢂCHPO), 16.57 (d,
CP